Benzoin-type copolymers and glass fabric laminates thereof



United States Patent Oflice ABSTRACT OF THE DISCLOSURE This inventionrelates to benzoin-type copolymers havwhere R can be as defined inFormula 1, in which the recurring units In and n can contain unlike Rgroups. The benzoin-type copolymers have utility as coatings and can becross-linked for bonding together layers of glass fabric.

This application is a divisional of application Ser. No. 328,099, filedDec. 4, 1963.

This invention relates to benzoin-type polymers. It is more particularlydirected to benzoin-type polymers having the structure where R can be a.a. a 3 a at) @Q Patented Dec. 31, 1968 By polymers is meant homopolymershaving the structure shown in Formula 1, and also the correspondingcopolymers having the structure claiiiliaiii L all.

where R can be as defined in Formula 1, in which the recurring units Inand n can contain unlike R groups. These recurring units can be arrangedin a random or ordered fashion.

Utility The polymers of the invention can be cured by heating them totemperatures of from 250 C. for periods ranging from several minutes toseveral hours. This heating causes the polymers to cross-link. Theresulting products have great thermal stability and high melting points,and are insoluble in such powerful solvents as dimethylformamide,dimethylsulfoxide, dimethylacetamide and hexamethylphosphoramide, evenon prolonged heating.

These properties make the polymers of the invention useful as resins forpreparing glass fabric laminates to be used in high temperatureapplications. The polymers are also useful in preparing heat stablefinishes on electrical apparatus and finishes on other articlessubjected to heat in use.

Glass fabric laminates can be made by first preparing a 20-60%, byweight, solution of an uncured polymer of the invention in a solventsuch as dimethylformamide. Glass fabric is impregnated with thissolution and the solvent is then evaporated at a temperature below thecure temperature of the polymer. The glass fabric is then laminated,under pressure, at a temperature of from 250 C. The resulting product isa rigid material, having a high degree of heat stability and greatresistance to tearing and fatigue on bending.

Coating compositions can be prepared from the polymers of the inventionby dissolving enough polymer in a suitable solvent such asdimethylformamide or dimethylsulfoxide to give a 10-50%, by weight,solution. This solution can then be applied by ordinary techniques tothe object to be coated. The solvent is evaporated to give a tough filmof the polymer. If desired, the coated object can be heated tocross-link the polymer and give a thermally-stable durable finish.

All polymers having the structure shown in Formula 1, where R, statedbroadly, is a divalent aromatic hydrocarbon radical or a divalentaromatic bis-hydrocarbon radical having an ether, thioether or alkylene(branched or straight chain) bridge are useful for the purposes justdescribed.

Preferred for these uses are polymers according to Formula 1 where R isa a. a

Most preferred because of the availability of the starting materialsused in preparing them are polymers according to Formula 1 where R is Apolymer corresponding to that shown in Formula 1 where R is has beenprepared by Jones and Tinker. This is set forth in J. Chem. Soc., 1955,1286. This polymer, however, is of low molecular weight and does notform a measurably viscous solution in dimethylformamide. The polymers ofthis invention, on the other hand, have relatively high molecularweights and have inherent viscosities, (0.5% solution indimethylformamide at 25 C.) greater than 0.05. These differences inmolecular weight and inherent viscosity spell the difference between apolymer which is useful for the utilities described and one which isnot.

Inherent viscosity is measured according to standard techniques asdescribed in polymer textbooks, e.g., W. R. Sorenson and T. W. Campbell,Preparative Methods of Polymer Chemistry, Interscience Publishers, Inc.,New vMi, st

Preparation of the polymers The polymers of the invention can beprepared according to the following illustrative equation:

where R is as described for Formula 1.

The dialdehyde reactants used in this reaction can be prepared accordingto the following general schemes:

In the method of Equation 3, a dialdehyde reactant is dissolved orsuspended in a suitable sol-vent, which is then heated for a time at atemperature up to about 150 C. The resulting solution contains thedesired polymer, which can be separated by precipitation if desired.

The reaction should be run in a medium which can dissolve the resultingpolymer. Such solvents as dimethylfor-mamide, dimethylsulfoxide,dimethylacetamide and hexamethylphosphoramide are suitable. If othermedia are used, low moleucular weight polymers precipitate prematurely.Such polymers are unsuited for the uses described.

It is essential that a cyanide salt catalyst be used to promotepolymerization. Such cyanide salts as sodium cyanide, potassium cyanide,lithium cyanide and barium cyanide are satisfactory. However, cyanidesalts which are derived from weak bases such as trimethylamine,triethylamine, triisopropylamine, monoethanol diethylamine, ammonia andsimilar bases give substantially faster reactions.

When cyanide salts derived from weak bases are used as catalysts, theycan be prepared in situ by adding hydrocyanic acid and the weak base tothe reaction mass. If a completely uncross-linked polymer is desired,the catalyst is prepared in this way using an HCN:base mol ratio of 1:5to 1:1. If a partially cross-linked polymer is desired, the catalyst isprepared using an HCNzbase mol ratio of from 111.1 to 1:15, or evenhigher.

In either event, the catalysts are used in the reaction atconcentrations of from 0.3 mol percent to 5 or even 10 mol percent,based on the aldehyde reactant. Preferably, the catalysts are used atconcentrations of 0.5 to 1.2 mol percent.

The polymerization itself can be carried out by dissolving or suspendinga dialdehyde reactant in a suitable reaction medium, to a concentrationof up to about 50% by weight. If a concentration greater than this isused, the viscosity of the solution after the polymer has been formedbecomes a problem. This solution or suspension is then heated to atemperature of up to about 150 C., and is held at that temperature forfrom /2 to hours.

After polymerization is complete, the cyanide catalyst should be removedby adding a small amount of acetic or formic acid to the solution. Thissolution can then be used directly for the utilities previouslydescribed.

If a solid polymer is desired, it can be obtained by precipitating itfrom solution with 10 volumes of water and filtering it off.

Alternatively, the polymers of the invention can be prepared by meltpolymerization. In this procedure, the aldehyde reactant is melted and0.5 to 5 mol percent of a cyanide catalyst, soluble in the moltendialdehyde phase, is added. Such a catalyst is tetraethylammoniumcyanide.

Melt-polymerization is carried out at a temperature ranging fromslightly above the melting point of the dialdehyde reactant up to about290 C. The time required for completion naturally depends on thetemperature used, but the reaction is generally complete in about twohours. Prolonged heating must be avoided if a polymer free ofcross-linking is desired.

The resultin polymer, after cooling to room temperature, is a solidwhich can be freed of the cyanide catalyst by powdering and washing itwith Water. This polymer can be readied for use by dissolving it in asuitable solvent.

The copolymers of Formula 2 can be prepared in essentially the samefashion, using a mixture of dialdehydes rather than only one.

The invention will be more easily understood and readily practiced byreferring to the following ilustrative examples:

Example 1 Fifty parts of terephthaldehyde are suspended in 100 parts ofdimethylformamide. This suspension is then blanketed with nitrogen andstirred at room temperature.

Two-tenths part of hydrocyanic acid and 0.35 part of triethylamine areadded to the suspension, which is then stirred at room temperature forabout 18 hours.

During this period, a homogeneous, light-brown, slightly viscoussolution forms. The reaction mixture is then heated for about 24 hoursat 45-50 C. to give a polymer having an inherent viscosity of 0.15(measured at 25 C. on a 0.5% solution of the polymer indimethylformamide.)

After 100 hours of heating, a polymer having an inherent viscosity of0.35 is obtained.

The cyanide catalyst is removed from the solution by adding 0.2-5 partsof acetic acid. This solution can then be used directly as a coatingcomposition.

If a solid polymer is desired, it can be precipitated from this solutionby adding the solution to 10 volumes of water. The resultinglight-yellow polymer can be filtered from the solution and dried at 60C.

This polymer has the structure hydes, in the same proportions, forterephthalaldehyde, and the listed reaction media for dimethylformamide:

CHO

E I. g Hm w: omo o o omo 8- omo omo mo 0 L J m l mo o l m m l mo 0 L n T2d omo w w omo 8 omo omo mo 0 L n m I mo 0 L B m I. 3 OHBOEQEQ w wQEQmOQQmQ fi eafi fin OmQO mOEOQOMQ mo 0 L m I omo 2 d omoll w w I! lomo gfiflfifi fia mo mo 0 l I H H l omo w w omo omo mo 0 on o L om onawa wamg omoa s; muflc hm m ww fi 363m 5 2 5 33a 2 53:20

Example 2 Ten parts of terephthalaldehyde are blanketed with nitrogenand then mixed with 0.15 part of tetraethylammonium cyanide. Afterheating for six hours at 196 C. under nitrogen, the reaction mixture isallowed to cool to room temperature. The resulting solid is powdered,washed with water and then dried to give a light-brown polymer havingthe structure This polymer has an inherent viscosity of 0.14 as measuredon a 0.5% solution in dimethylformamide at 25 C.

Example 3 A 30% solution of the polymer prepared in Example 1 indimethylformamide is sprayed on a glass plate. The dimethylformamide isallowed to evaporate and the plate is then heated to 250 C. for from tominutes.

The resulting clear film is insoluble in dimethylformamide and does notmelt at temperatures up to 500 C.

Example 4 Twenty-five parts of terephthalaldehyde and parts ofisophthalaldehyde are suspended in 50 parts of dimethylformamide and thesolution is blanketed with nitrogen. Two parts of HCN and 3.5 parts oftriethylamine are then added to the reaction mixture.

After several hours of stirring at room temperature, the reactionmixture becomes homogeneous and slightly viscous. This mixture isstirred for 18 more hours and then heated at 45 C. for an additional 18hours.

The resulting viscous solution can be used directly as a coatingcomposition, or if the solid polymer is desired, it can be obtained byprecipitating it with 500 parts of methanol .or water, filtering it oifand drying it.

The structural formula of this copolymer is CT ii iL L 1'1 |n Example 5A 25% solution of the polymer prepared in Example 1, indimethylformamide, is applied to a glass fabric by dipping. The solventis then evaporated at 100l5() C.

A 10-ply laminate is prepared from this impregnated glass fabric bylayering it and pressing the layers together at a pressure of 200 psi.and a temperature of 250 C.

This laminate has excellent heat stability and resistance to tearing.

What is claimed is:

1. A copolymer selected from the group consisting of random copolymersand ordered copolymers having the structure where R is selected from thegroup consisting of (porn 03 03 QM (we,

x W W and References Cited UNITED STATES PATENTS 3,166,532 1/1965 Sweeny26067 3,215,675 11/ 1965 Koral et al. 26067 OTHER REFERENCES Jones etal.: J. Chem. Soc. (London) pp. 1286 and 1287, (1955).

Gillman: Organic Chem., An Advanced Treatise, vol. 3, Pub. by John Wileyand Sons, Inc., NY. (1953) pp. 111 and 112.

ROBERT F. BURNETT, Primary Examiner.

WILLIAM J. VAN BALEN, Assistant Examiner.

U.S. Cl. X.R. 117126; 26067

